Titanium nitride films are extremely important in a wide variety of applications due to its different characteristics such as extreme hardness, abrasion resistance, high melting temperature, high corrosion resistance and electrical conductivity. For example, titanium nitride films are used as wear-resistant coatings for cutting tools and other mechanical parts, and for high temperature structural materials, in the microelectronic industry, for use as diffusion barriers in electronic devices, particularly against diffusion between aluminum and silicon, and as planarization and interconnect material, particularly in multi-level metallization schemes.
A review of technical literature in the past several years shows that there is great interest in new coatings and surface treatment, particularly in use of titanium nitride for forming films Titanium nitride films prepared on silicon are widely used as diffraction barrier layers in large-scale integrated circuits. TiN film is also remarkably hard and is used as a wear-resistant coating on tools since it decreases the rate of abrasive wear during the cutting process as well as the chemical interaction between the tool and the work piece because of its chemical inertness. TiN is a very stable compound that enhances the pitting resistance of many substrate materials in most environments.
There are a wide variety of techniques for synthesizing titanium nitride films on different substrates. Prior techniques for synthesizing titanium nitride films include chemical vapor deposition and sputtering (H. Itoh et al., “Chemical Vapour Deposition of Corrosion-Resistant TiN Film to the Inner Walls of Long Steel Tubes,” J. Mat. Sci., 21, 751-56 (1986) and D. S. Williams et al., “Nitrogen, Oxygen, and Argon Incorporation During Reactive Sputter Deposition of Titanium Nitride,” J. Vac. Sci. Technol. B, 5, 1723-29 (1987)).
It is also known in the art to use ion implantation to apply a titanium nitride film to the surface of a substrate (B. Rauschenbach, “Formation of Compounds by High-Flux Nitrogen Ion Implantation in Titanium,” J. Mat. Sci., 21, 395-404 (1986), M. Belii et al., Formation of Chemical Compounds by Ion Bombardment of Thin Transition Metal Films,” Phys. Status Solidi A, 45, 343-52 (1978), and P. A. Chen et al., “Titanium Nitride Films Prepared by Ion Implantation,” Thin Solid Films, 82, L91-92 (1981)).
It is also known in the art to use pyrolysis of preceramic polymers resulting in synthesis of titanium nitride films by slow heating of sol-gel derived titanium oxide films in ammonium gas (D. Seyferth et al., “Preparation of Titanium Nitride and Titanium Carbonitride by the Pre-ceramic Polymer Route,” J. Mat. Sci. Lett., 7, 487-88 (1988)). Kamiya, et al., “Nitridation of the Sol-gel Derived Titanium Oxide Films by Heating in Ammonia Gas”, J. Am. Cerm. Soc., 73, 2750-52 (1980)).
However, the above procedures are subject to limitations dictated often by the size or shape of the substrate. These limitations limit the use of titanium nitride films particularly where planarization and/or the filling of vias in multilevel metallization are required. Another disadvantage of these methods is that the resulting titanium nitride films may contain high levels of impurities, such as oxygen, which in turn adversely affect the desired characteristics of the final product. For example, the level of oxygen in the nonstoichiometric films deposited by Kamiya et al result in decreased conductivity and decreased barrier efficiency.
The thermal growth method for film formation/deposition on a substrate comprises heating the wafer substrate at temperatures which are controlled very precisely, typically between 800 and 1200° C., with a choice of ambient gases. The high temperature promotes the reaction between the ambient gas and the wafer substrate. For instance, films of silicon dioxide are often produced by this method. The problem with this method is the extremely high deposition temperatures required. Extremely high temperatures are a concern for two reasons. First, high temperature may be incompatible with or even detrimental to other elements of the integrated circuit, and, second, excessive cycling from low to high temperatures can damage a circuit, thereby reducing the percentage of reliable circuits produced from a wafer. Therefore, a lower deposition temperature is always preferred so that the characteristics of the deposited film are unaffected. As a result, the thermal growth method is not preferred for the formation of TiN films particularly in the case of IC's.
In sputter deposition, the material to be deposited is bombarded with positive inert ions. If the energy of the incident ions exceeds the surface binding energy, atoms are ejected into the gas phase where they are subsequently deposited on to the substrate, which may or may not be negatively biased. Sputter deposition has been widely used in integrated circuit processes to deposit titanium-containing films. The primary disadvantage of sputter deposition is that it results in films having poor step coverage, so it may not be widely useable in submicron processes. Films deposited by sputter deposition on slanted or vertical surfaces do not exhibit uniform thickness, and the density of films deposited on these surfaces is usually not as high as the films deposited on horizontal surfaces.
In spin-on deposition, the material to be deposited is mixed with a suitable solvent and spun on to the substrate. The primary disadvantage of spin-on deposition is that nominal uniformity can only be achieved at relatively high thicknesses. Therefore, this method is primarily used for the deposition of photoresist and the like. It is generally not useful for the deposition of thin films.
Of the various methods discussed above, chemical vapor deposition and plasma enhanced chemical vapor deposition are suitable for formation of the thinnest films with a greater degree of uniformity.
In CVD, the gas phase reduction of highly reactive chemicals under low pressure results in very uniform thin films. A basic CVD process used for depositing titanium containing compound involves a given composition of reactant gases and a diluent which are injected into a reactor containing one or more silicon wafers. The reactor is maintained at selected pressures and temperatures sufficient to initiate a reaction between the reactant gases. The reaction results in the deposition of a thin film on the wafer. If the gases include hydrogen and a titanium precursor, a titanium-containing film will be deposited. For example, if, in addition to hydrogen and the titanium precursor, the reactor contains a sufficient quantity of nitrogen or a silane, the resulting titanium-containing film will be titanium nitride and titanium silicide respectively. Plasma enhanced CVD is a form of CVD that includes bombarding the material to be deposited with a plasma to generate chemically reactive species at relatively low temperatures.
Chemical vapor deposition is typically carried out in one of two types of reactors. One type of reactor is called a hot wall reactor. A hot wall reactor is operated at a low pressure, typically 1 Torr or less, and high temperatures, typically 600° C. or greater. The other type of reactor is called a cold wall reactor. A cold wall reactor is operated at atmospheric pressure and low temperatures, typically 400 to 600° C.
Films produced by these techniques, however, often exhibit poor adhesion to the substrate. Coupled with this problem is the requirement of high deposition temperature (>500° C.) for effective formation of TiN film and relatively long duration of time required for thin film formation. In many of these techniques, the plasma dimensions, and subsequently, substrate size also limit the process of film deposition.
U.S. Pat. No. 4,514,437 to Prem Nath, issued Apr. 30, 1985, discloses a method and apparatus for depositing thin films, such as indium tin oxide, onto substrates. The deposition comprises one step in the fabrication of electronic, semiconductor and photovoltaic devices. An electron beam is used to vaporize a source of solid material, and electromagnetic energy is used to provide an ionizable plasma from reactant gases. By passing the vaporized solid material through the plasma, it is activated prior to deposition on to a substrate. In this manner, the solid material and the reactant gases are excited to facilitate their interaction prior to the deposition of the newly formed compound on to the substrate.
U.S. Pat. No. 4,944,961 to Lu et al., issued Jul. 31, 1990, describes a process for partially ionized beam deposition of metals or metal alloys on substrates, such as semiconductor wafers. Metal vaporized from a crucible is partially ionized at the crucible exit, and the ionized vapor is drawn to the substrate by an imposed bias. Control of substrate temperature is said to allow non-conformal coverage of stepped surfaces such as trenches or vias. When higher temperatures are used, stepped surfaces are planarized. The examples given are for aluminum deposition, where the non-conformal deposition is carried out with substrate temperatures ranging between about 150° C. and about 200° C., and the planarized deposition is carried out with substrate temperatures ranging between about 250° C. and about 350° C.
U.S. Pat. No. 4,976,839 to Minoru Inoue, issued Dec. 11, 1990 discloses a titanium nitride barrier layer of 500 Å to 2,000 Å in thickness formed by reactive sputtering in a mixed gas including oxygen in a proportion of 1% to 5% by volume relative to the other gases, comprising an inert gas and nitrogen. The temperature of the silicon substrate during deposition of the titanium nitride barrier layer ranged between about 350° C. and about 500° C. during the sputtering, and the resistivity of the titanium nitride film was “less than 100 μΩ-cm”, with no specific numbers other than the 100 μΩ-cm given.
S. M. Rossnagel and J. Hopwood describe a technique of combining conventional magnetron sputtering with a high density, inductively coupled RF plasma in the region between the sputtering cathode and the substrate in their 1993 article titled “Metal ion deposition from ionized magnetron sputtering discharge”, published in the J. Vac. Sci. Technol. B. Vol. 12, No. 1, January/February 1994. One of the examples given is for titanium nitride film deposition using reactive sputtering, where a titanium cathode is used in combination with plasma formed from a combination of argon and nitrogen gases. The resistivity of the films produced ranged from about 200 μΩ-cm to about 75 μΩ-cm, where higher ion energies were required to produce the lower resistivity films. The higher the ion energy, the more highly stressed the films, however. Peeling of the film was common at thicknesses over 700 Å, with depositions on circuit topography features delaminating upon cleaving.
U.S. patent application Ser. No. 08/511,825 of Xu et al. filed Aug. 7, 1995, assigned to the Assignee of that invention, and incorporated by reference in its entirety, describes a method of forming a titanium nitride-comprising barrier layer which acts as a carrier layer. The carrier layer enables the filling of apertures such as vias, holes or trenches of high aspect ratio and the planarization of a conductive film deposited over the carrier layer at reduced temperatures compared to prior art methods.
U.S. Pat. No. 5,202,152 discloses that a substantially stoichiometric film of titanium nitride is provided by heating a substrate upon which a solution containing titanium has been applied at a substantially ambient temperature to provide a gel-film containing titanium on the surface of the substrate in an ammonia atmosphere. The substrate is heated to a temperature at which the titanium in the titanium-containing gel-film is substantially completely transformed to a substantially stoichiometric titanium nitride film, and at a rate of temperature change that is great-enough to prevent the formation of nonstoichiometric titanium nitride compounds or other undesired titanium compounds in the resulting titanium nitride film.
While there are several references in the art to the manufacture of TiN stoichiometric films as well as non-stoichiometric films, it has hitherto been believed that non-stoichiometric films would not be usable due to several disadvantages such as decrease in corrosion resistance, difficulty in deposition, formation of stoichiometric phase during annealing, difficulty in controlling operational parameters required to maintain characteristics of the TiNx films such as resistivity, thickness and the like. It was also believed that the film quality of non-stoichiometric films formed in the art show ‘pin holes’ reflecting expected columnar growth processes and therefore would not be usable for most applications.